The role of atomic quadrupoles in intermolecular electrostatic interactions of polar and nonpolar molecules
The role of atomic quadrupoles in intermolecular electrostatic interactions of polar and nonpolar molecules
复制标题
原子四极杆在极性和非极性分子的分子间静电相互作用中的作用
DOI：
10.1063/1.1585016
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发表时间：
2003
影响因子：
4.4
通讯作者：
H. Torii
中科院分区：
文献类型：
--
作者：
H. Torii
为了深入了解在一些常用溶剂中观察到的具有大偶极导数模式的异常振动频移的原因，研究了原子四极在一些含卤素分子（CX4， HX和X2， X=F， Cl和Br）， CH4， CO2和CS2的分子间静电相互作用中的作用。通过对分子周围静电电位的拟合，氯、溴和硫原子获得了大的原子四极，这表明原子四极效应对于元素周期表中第三行和更高行共价键原子周围的静电相互作用是重要的。以氯原子为例，考察了CCl4、HCl和Cl2原子内部的电子密度。发现这些电子密度具有高度的各向异性。这种电子密度的各向异性可以用已占据分子轨道的形式来合理地解释，并且被认为是一种有效的方法。
For the purpose of getting insight into the reason for the anomalous vibrational frequency shifts observed in some usually used solvents for a mode that has a large dipole derivative, the role of atomic quadrupoles in intermolecular electrostatic interactions is studied for some halogen-containing molecules (CX4, HX, and X2 with X=F, Cl, and Br), CH4, CO2, and CS2. From the fitting to the electrostatic potentials around the molecules, large atomic quadrupoles are obtained for the chlorine, bromine, and sulfur atoms, suggesting that the atomic quadrupolar effect is important for electrostatic interactions around covalently bonded atoms on the third and higher rows in the periodic table. Taking the case of the chlorine atoms as an example, the electron densities inside the atoms in CCl4, HCl, and Cl2 are examined. It is found that these electron densities are highly anisotropic. This anisotropy in electron densities is reasonably explained by the forms of the occupied molecular orbitals, and is considered t...
影响因子：
3.3
作者：
Fox, T;Kollman, PA
通讯作者：
Kollman, PA